Film ozonolysis in a tubular or multitubular reactor

ABSTRACT

The disclosure relates to a method of performing ozonolysis or ozone-based oxidation on a liquid or emulsified reagent using a tubular falling film reactor with one or multiple tubes wherein the combined ozone and carrier gas flow is co-current.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/015,311, filed Jun. 20, 2014, and U.S. Provisional Application No.62/163,022, filed May 18, 2015, both of which are incorporated herein byreference in their entireties.

BACKGROUND

Ozonolysis or ozone-based oxidation of reagents currently in use in thechemical industry generally rely on processing large amounts of materialin either tray-type continuous ozonation systems or in batch systems,e.g., U.S. Pat. No. 2,813,113. The use of either type of establishedmethod, however, results in the accumulation of peroxide intermediatesthat can be unstable and present a significant explosion risk.Alternatively, processing small amounts of material in a continuousfashion can significantly reduce these risks. Solutions to address thisimportant safety issue include the use of microstructured falling filmreactors such as those described in U.S. Pat. No. 7,825,277 B2, andavailable from ThalesNano, Inc. These technologies, however, have notbeen adapted for use in large-scale (multi-ton) manufacturing processes,owing to challenges with throughput and the operation costs associatedwith maintaining large numbers of reaction vessel channels and preciselycalibrated instruments.

Other commercial reaction technologies use sparging or aerationtechniques to drive interactions between liquid and gaseous reagents,which can introduce local hot spots and requires that the gaseousreagent be present at high pressures. The disclosure described hereinaddresses the need for a method of industrial-scale ozonolysis that issafer and more efficient than conventional methods.

SUMMARY OF THE DISCLOSURE

The approach to ozonolysis described herein functions using gravityassisted co-current reagent flow to facilitate gaseous reagent diffusioninto a liquid or emulsified reagent, which simplifies the reaction setupand minimizes the mechanical energy required, all while achieving ascalable and continuous process that does not allow for the accumulationof large amounts of hazardous intermediates, thus rendering the processand equipment described herein suitable for large, industrial-scaleozonolysis.

In one embodiment of the current disclosure a monotubular ormultitubular reactor is used for ozonolysis or ozone-based oxidation inwhich:

-   -   (a) homogeneity of the reagent-containing film and thermal        exchange is maximized,    -   (b) selection of the optimum size of the individual tubes is        based on the best compromise between maximum internal diameter        (for optimum throughput) and minimum height (for reduced head        loss) while maintaining mechanical simplicity (for reduced        maintenance), and    -   (c) distribution of the gaseous ozone-containing reagent with        negligible head loss is conditioned by the reagent-containing        film thickness and corresponding flow rate such that the        conversion and temperature profiles are optimized along the tube        length.

The parameters above can be optimized both theoretically andempirically, and can be used to ensure excellent results without theneed for calibration when changing the flow rate and/or composition ofthe liquid or emulsified reagent.

In some embodiments, the method of performing ozonolysis or ozone-basedoxidation on a liquid or emulsified reagent entails using a tubularfalling film reactor with one or multiple tubes wherein the combinedozone and carrier gas flow is co-current.

In some embodiments, the diameter of the tube(s) is between 5 mm and 5m.

In some embodiments, the diameter of the tube(s) is between 5 mm and 50mm.

In some embodiments, the diameter of the tube(s) is between 5 mm and 30mm.

In some embodiments, the diameter of the tube(s) is between 10 mm and 25mm.

In some embodiments, the diameter of the tube(s) is 25 mm.

In some embodiments, the diameter of the tube(s) is 10 mm.

In some embodiments, the diameter of the tube is between 50 mm and 5 m.

In some embodiments, the diameter of the tube is between 0.5 m and 5 m.

In some embodiments, the diameter of the tube is between 50 mm and 5 mand an annular element is added to the center of the tube to regulategas flow and to add additional film surface area.

In some embodiments, the length of the tube(s) is between 1 and 20 m.

In some embodiments, the length of the tube(s) is between 1 and 7 m.

In some embodiments, the length of the tube(s) is 1.7 m.

In some embodiments, the length of the tube(s) is 6 m.

In some embodiments, the length of the tube(s) is between 7 and 20 m.

In some embodiments, the distribution of gas within the tube(s) may becontrolled by annular spaces for gas flow within the tube(s).

In some embodiments, multiple falling film tube reactors are used inseries to process a continuous stream of liquid or emulsified reagent.

In some embodiments, the method of performing ozonolysis or ozone-basedoxidation on a liquid or emulsified reagent with a gaseous reagent(e.g., comprising ozone and one or more carrier gases) includes:

-   -   (a) feeding the liquid or emulsified reagent from a common        liquid or emulsified reagent feeding chamber that is maintained        completely full through annular slots and into a plurality of        parallel and substantially identical tubes, as to form a liquid        or emulsified reagent film on the internal surface of each tube;    -   (b) feeding the gaseous reagent through the annular slots and        into the tubes from a gaseous reagent feeding chamber, the        feeding pressure of the gaseous reagent being substantially the        same as the pressure loss from the gaseous reagent flow through        the tubes containing the liquid or emulsified reagent film, but        less than the feeding pressure of the liquid reagent;    -   (c) cooling the tubes by flowing a liquid coolant through a        housing surrounding the tubes; and    -   (d) collecting reaction product(s) and gaseous reagent exhaust        in one or more product containers connected to the end of the        tubes opposite that connected to the annular slots.

In some embodiments, the length of the tubes used in this method isbetween 1 and 20 m.

In some embodiments, the length of the tubes used in this method isbetween 1 and 7 m.

In some embodiments, the length of the tubes used in this method is 1.7m.

In some embodiments, the length of the tubes used in this method is 6 m.

In some embodiments, the length of the tubes used in this method isbetween 7 and 20 m.

In some embodiments, the internal diameter of the tubes used in thismethod is between 5 mm and 5 m.

In some embodiments, the internal diameter of the tubes used in thismethod is between 5 mm and 50 mm.

In some embodiments, the internal diameter of the tubes used in thismethod is between 5 mm and 30 mm.

In some embodiments, the internal diameter of the tubes used in thismethod is between 10 mm and 25 mm.

In some embodiments, the internal diameter of the tubes used in thismethod is 25 mm.

In some embodiments, the internal diameter of the tubes used in thismethod is 10 mm.

In some embodiments, the internal diameter of the tubes used in thismethod is between 50 mm and 5 m.

In some embodiments, the internal diameter of the tubes used in thismethod is between 0.5 m and 5 m.

In some embodiments, the feeding pressure of the gaseous reagent used inthis method is between 0.1 and 5 bar.

In some embodiments, the feeding pressure of the gaseous reagent used inthis method is between 0.1 and 0.5 bar.

In some embodiments, the feeding pressure of the gaseous reagent used inthis method is between 0.2 and 0.4 bar.

In some embodiments, the feeding overpressure of the liquid oremulsified reagent with respect to the feeding pressure of the gaseousreagent is between 5 and 15 cm of liquid column.

In some embodiments, the carrier gas contains, at least in part, gaseousreagent exhaust from one or more product containers.

In some embodiments, the reagent is a liquid.

In some embodiments, the reagent is an emulsion in water.

In some embodiments, the liquid or emulsified reagent or reagent mixtureis the starting material which is reacted with ozone to yield oxidizedproduct(s).

In some embodiments, the starting material is an alkene, alkyne, or anyother compound that may be oxidized with ozone.

In some embodiments, the liquid or emulsified reagent compriseshydroxycitronellene, methoxycitronellene, rose ketones (e.g., Ionone),fatty acid methyl esters (FAME), triglycerides, fatty acids, fattyalcohols, fatty esters, diterpenes, sesquiterpenes, monoterpenes, allylethers, alpha olefins, rosin acids, tertiary amines, alkanes, amides,carboxylic acids, or compounds containing an aromatic ring.

In some embodiments, the reagent introduced into the reactor is anycompound that is susceptible to ozone oxidation. In some embodiments,the reagent comprises any alkane, amide, carboxylic acid, or aromaticring.

In some embodiments, the reaction products may be further reduced oroxidized to generate corresponding carbonyls, alcohols, and/or acids.

In some embodiments, the liquid or emulsified reagent compriseshydroxycitronellene.

In some embodiments, the liquid or emulsified reagent is ahydroxycitronellene emulsion in water.

In some embodiments, the liquid or emulsified reagent is ahydroxycitronellene solution in methanol.

In some embodiments, the product of the method described herein ishydroxymelonal.

In some embodiments, the liquid or emulsified reagent comprisesmethoxycitronellene.

In some embodiments, the liquid or emulsified reagent is amethoxycitronellene emulsion in water.

In some embodiments, the liquid or emulsified reagent is amethoxycitronellene solution in methanol.

In some embodiments, the product is methoxymelonal.

In some embodiments, the liquid or emulsified reagent comprises fattyacid methyl esters (FAME).

In some embodiments, the liquid or emulsified reagent is a FAME emulsionin water.

In some embodiments, the liquid or emulsified reagent is a FAME solutionin methanol.

In some embodiments, the product produced by the method described hereincomprises methyl azealdehyde and nonanal.

In some embodiments, the liquid or emulsified reagent comprises anunsaturated olechemical such as a triglyceride, a fatty acid, a fattyalcohol, or a fatty acid ester.

In some embodiments, the liquid or emulsified reagent comprises aditerpene such as abietic acid or its ester.

In some embodiments, the liquid or emulsified reagent comprises a mono-or di-unsaturated sesquiterpene.

In some embodiments, the liquid or emulsified reagent comprises a mono-or di-unsaturated monoterpene or terpene derivative such as pinene orlimonene.

In some embodiments, the liquid or emulsified reagent comprises an allylether of 10 to 30 carbon atoms.

In some embodiments, the liquid or emulsified reagent comprises an alphaolefin of 10 to 30 carbon atoms.

In some embodiments, the liquid or emulsified reagent comprises a roseketone. In some embodiments the rose ketone is Ionone.

In some embodiments, the product of the method described herein iscyclocitral.

In some embodiments, the liquid or emulsified reagent comprises atertiary amine.

In some embodiments, the product of the method described herein is anN-oxide derivative.

In some embodiments, the carrier gas is O₂.

In some embodiments, the carrier gas is a mixture of O₂ and N₂. In someembodiments, the carrier gas is about 95% O₂ and 5% about N₂, about 90%O₂ and about 10% N₂, about 85% O₂ and about 15% N₂, about 80% O₂ andabout 20% N₂, about 70% O₂ and about 30% N₂, about 60% O₂ and about 40%N₂, about 50% O₂ and about 50% N₂, about 40% O₂ and about 60% N₂, about30% O₂ and about 70% N₂, about 20% O₂ and 80% N₂, or 10% O₂ and 90% N₂,wherein the term “about” refers to the indicated percentage +/−2.5%.

In some embodiments, the carrier gas is about 95% O₂ and about 5% N₂.

In some embodiments, the carrier gas is air.

In some embodiments, the liquid or emulsified reagent comprises analkene.

In some embodiments, the liquid or emulsified reagent comprises analkyne.

In some embodiments, the primary component of the liquid or emulsifiedreagent is methyl oleate.

In some embodiments, the liquid or emulsified reagent is derived fromsoy.

In some embodiments, the liquid or emulsified reagent is derived frompalm oils.

In some embodiments, the liquid or emulsified reagent is derived fromalgal oils.

In some embodiments, waste water can be the reagent introduced into thereactor for the purpose of treating the water.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram of the vertical cross-section of a multitubularreactor.

FIG. 2 is a diagram of the detail denoted by II in FIG. 1, on a largerscale.

FIG. 3 is a diagram of the cross-section along line III-III in FIG. 1.

DETAILED DESCRIPTION OF THE DISCLOSURE

The disclosure relates to the ozonolysis or ozone-related reactionswhich occur on the free surface of a film of a liquid or emulsifiedreagent or reagent mixture that is subject to the controlled amount of agaseous reagent comprising ozone (O₃). The liquid or emulsified reagentor reagent mixture is the starting material which is reacted with ozoneto yield oxidized product(s). The starting material is generally analkene, alkyne, or any other compound that may be oxidized with ozone.The reaction products may be further reduced or oxidized to generatecorresponding carbonyls, alcohols, and/or acids.

Performing ozone-based oxidation reactions in industrial-scale tubularfalling film reactors (e.g., those originally designed for otherprocesses, such as sulfonation) is advantageous for a variety ofreasons. For example, tubular falling film sulfonation reactors operateby exposing relatively small volumes of liquid reagent(s) to relativelyhigh volumes of reactive gaseous reagent(s) that have been diluted withan inert carrier gas or mixture thereof. Due to their continuous mode ofoperation, the reactors are efficient and exhibit reasonably highthroughput rates per reactor tube, but do not allow for the accumulationof intermediates. Moreover, these reactors handle exothermic processeswell because they include excellent heat dissipation features. Themethod described herein provides a safe and efficient means ofperforming ozonolysis reactions on an industrial scale by takingadvantage of the aforementioned benefits of tubular falling filmsulfonation reactors.

Examples of tubular falling film sulfonation reactors are described inGB 2,043,067 B, which is incorporated herein by reference. Tubular ormultitubular co-current reactors are particularly useful due to theirrelatively low cost and mechanical simplicity. Such reactors can beadapted to use for ozonation reactions.

An additional safety advantage can be realized over traditionalozonolysis approaches if the reaction is carried out in water or as anemulsion with water. The flashpoint of the liquid reagent(s) can beeliminated or dramatically reduced in the presence of water, therebyminimizing the risk of fire in the event of an uncontrolled exotherm orexplosion. Furthermore, the use of an emulsion allows for easier controlof the liquid reagent in terms of concentration, distribution within theozonolysis device tubes, and temperature.

As shown in FIGS. 1-3, the reactor 1 contains a set of parallel tubes 10enclosed in a cylindrical housing, which is connected at one end to agaseous reagent feeding chamber 70 and at the other end to a productcollection chamber 40.

Gaseous ozone from an external source, such as a corona discharge orelectrolysis driven ozone generating device, flows through conduit 12into the feeding chamber 70 where it enters the tubes 10 and reacts withthe liquid or emulsified reagent.

Reaction product(s) emerge from the tubes 10 into the product collectionchamber 40, from which the reaction product(s) are removed via conduit13 and collected in an external vessel.

A liquid coolant, such as water and/or glycol, flows into the reactorhousing through conduit 20, around the tubes 10 and out of the reactorhousing via conduit 21. Alternatively, the liquid coolant flows into thereactor housing through conduit 21 and out via conduit 20. The inconduit 20 and out conduit 21 direction of flow for the liquid coolantis preferred, however, because the exothermic reaction between ozone andthe liquid or emulsified reagent(s) takes place preferentially at theportion of the tubes 10 that is closest to the feeding chamber 70.Numerous diaphragms 22, located inside the reactor housing and orientedperpendicular to the tubes 10, increase alter the path and increase theturbulence of the coolant flowing through the reactor housing. Thecoolant is separated from the gas feeding chamber and the productcollection chamber by plates 23 and 24, respectively, which are orientednormal to, and positioned at the ends of the tubes 10.

Additional configurations for cooling the reactor that are not depictedin FIGS. 1-3 are also effective and may be employed. For example, thereactor housing interior may contain two separate cooling sections, oneto cool the end of the tubes 10 that is connected to the feeding chamber70 and one too cool the end of the tubes 10 that is connected to theproduct collection chamber 40, to enhance the overall cooling capacity.

A third tube plate 25 is positioned between the gas feeding chamber 70and plate 23 such to define a feeding chamber 15 for the liquid oremulsified reagent(s). One or more conduits 16 are used to feed theliquid or emulsified reagent(s) into the feeding chamber 15, which alsocontains a device as shown in FIG. 2 for introducing the liquid oremulsified reagent(s) into one end of the tubes 10.

As shown in FIG. 2, each tube 10 has a cylindrical portion 30 with aslightly larger diameter than the remainder of the tube, which isconnected to the tube by a frusto-conical section 31. The cylindricalportion 30 contains passages 38 for introducing the liquid or emulsifiedreagent(s) into the tube 10. The cylindrical portion 30 fits, withsuitable clearance, in a cylindrical sleeve 33, the latter of whichfacilitates for the formation of liquid-tight seals between thecylindrical portion 30 and plates 23 and 25. The cylindrical sleeve 33contains passages 36 for the liquid or emulsified reagent(s), ofsuitable size and circumferential distribution as not to generate headlosses when allowing passage of the liquid or emulsified reagent(s) intothe cylindrical portion 30.

The outer surface of a second sleeve 50 is in contact with the innersurface of the cylindrical portion 30, except for a central section,owing to the presence of a wide annular groove 51. The inner surface ofthe cylindrical portion 30 and groove 51 define an annular space forreceiving the liquid or emulsified reagent(s) that enter the tube 10from the passages 36 and 38, which open into groove 51. A seal groove 34is positioned between the cylindrical sleeve 33 and the frusto-conicalsection 31. Suitable axial passages 52, shown only diagrammatically inFIG. 2, allow the liquid reagent to discharge into the tube interiorfrom the annular space defined by groove 51. The sleeve 50 comprises abeveled or frusto-conical end with the same opening angle as thefrusto-conical section 31.

Between one end of the second sleeve 50 and the frusto-conical section31 there is an annular slot oriented according to the generatrices of atruncated cone, the width of this slot being defined by the gap spacebetween sleeve 50 and the frusto-conical section 31. The gap spacebetween sleeve 50 and the frusto-conical section 31 may be adjusted by athreaded crown 54 screwed into the end of the cylindrical portion 30that is closest to the gas feeding chamber 70. It is thus possible, byscrewing up or down the sleeve 50 in the cylindrical portion 30, toadjust the cross-section of the annular slot between the edge of thesleeve 50 and the frusto-conical section 31. The annular slot, beingorientated according to the generatrices of a cone, favors thedistribution of the liquid reagent in the form of a film entirely aroundthe inner surface of the tube 10.

The inner diameter of sleeve 50 is suitably the same as the innerdiameter of the tube 10 so that the gaseous reagent coming from thedistribution chamber 70 may be brought to brush the free surface of thefilm 60 without resulting in a significant head loss.

Starting materials for the method described herein include any compoundthat may be oxidized by ozonolysis. Specific examples of startingmaterials for this process include hydroxycitronellene,methoxycitronellene, fatty acid methyl esters (FAME), triglycerides,fatty acids, fatty alcohols, fatty esters, diterpenes, sesquiterpenes,monoterpenes, allyl ethers, alpha olefins, and rosin acids.

In one embodiment, a tube reactor for ozonolysis includes a tube (see,e.g., 10 in FIG. 1) with a 5 to 30 mm internal diameter (e.g., 10 mm)and a length of 1 to 7 m (e.g., 1.7 m). The tube is constructed of asuitable material (e.g., stainless steel) and is connected to a gaseousreagent feeding chamber (see, e.g., 70 in FIG. 1) that allows gas toflow through the center of the tube and liquid to be flowed in a film onthe wall of the tube through annular slots (e.g., as shown in FIG. 2;component II in FIG. 1). The tube is enclosed in a jacket (see, e.g., 1in FIG. 1) for circulating liquid coolant around it (see, e.g., 10 inFIG. 1), with the end of the tube protruding through a liquid-sealedorifice (see, e.g., 24 in FIG. 1). A liquid/gas separation vessel isconnected to the bottom of the reaction tube (see, e.g., 10 in FIG. 1).The excess gas flows into an ice condenser and then into an ozonedestruction unit. The collected liquid product is pumped into samplingcontainers for analysis by a peristaltic pump.

In one embodiment, the gas inlet (see, e.g., 12 in FIG. 1) is connectedto an ozone generator, and the liquid inlet is connected to a stirredfeed tank equipped with a peristaltic pump. The liquid inlet pipe isalso jacketed and cooled to control the temperature of the feed liquidor emulsified reagent.

In one embodiment, for emulsion preparation, water is combined with theorganic reagent in a ratio (e.g., 5:1) ranging from stoichiometric(i.e., 1:1) to very dilute (e.g., 100:1) in the feed tank and stirredvigorously such that a homogenous emulsion is maintained. Deionizedwater is used for the emulsions.

In one embodiment, a mixture of O₂ and N₂ gas is used to feed the ozonegenerator and to comprise the ozone carrier gas for the ozonolysisreaction.

In one embodiment, conversions of starting materials are determined bygas chromatography (GC) and are calculated on the basis of thedisappearance of starting material. Samples are prepared by extractingthe organic components of the emulsion into a homogenous organic solventphase. Analysis of the composition of the aforementioned organic phaseis accomplished by gas chromatography.

In one embodiment, the ratio of water to organic reagent ranges from 1:1to 100:1 (e.g., 5:1), the ozone concentration ranges from 2.5% to 10%(e.g., 5%), the gas flow rate ranges from 10 to 20 L/min (e.g., 15L/min), the ozone mass flow rate ranges from 32.6 to 135 g/h (e.g., 65.9g/h), the emulsion flow rate ranges from 1 to 5 kg/h (e.g., 2 kg/h), andthe cooling temperature ranges from 0 to 20° C. (e.g., 10° C.), to yieldstarting material conversion percentages ranging from 13.70% to 52.63%(e.g., 26.76%).

In another embodiment, 1-6 pilot tube reactors (e.g., 3) can beconnected in series, with gas and liquid being separated at the bottomof each tube. Tubes can be from 1-6 m in length (e.g., 1.7 m), and thetubes can range in diameter from 5-50 mm (e.g., the first 2 tubes being25 mm in diameter and the 3^(rd) tube being 10 mm in diameter). Theorganic liquid feed can be flowed in a solution of reagent and nonanoicacid in ranges from 1:1 to 100:1 (e.g., 3:1) through the first tube tothe second and third tube in series at rates ranging from 1-99 kg/hr(e.g., 4.2 kg/hr). The gas can be flowed co-currently at ozoneconcentration in ranges from 0.5% to 10% (e.g., 5.1%) from the 3^(rd)tube through the 2^(nd) to the 1^(st) tube at a flow rate from 10 to1500 L/min (e.g., 150 L/min), and the cooling jacket temperature can bemaintained between 0 and 50° C. (e.g., 15° C.) to yield conversionpercentages between 93-100% (e.g., 97.6%).

EXAMPLES Example 1 Film Ozonolysis in a Monotubular Reactor OzonolysisReactor Details

A pilot tube reactor was used for ozonolysis, including a tube with a 10mm internal diameter and a length of 1.7 m (e.g., 10 in FIG. 1). Thetube was constructed of 316 stainless steel and was connected to agaseous reagent feeding chamber (e.g., 70 in FIG. 1) that allowed gas tobe flowed through the center of the tube and liquid to be flowed in afilm on the wall of the tube through annular slots (e.g., as shown inFIG. 2; component II in FIG. 1). The tube was enclosed in a steel jacket(e.g., 1 in FIG. 1) for circulating cooling fluid around the reactiontube (e.g., 10 in FIG. 1) with the end of the tube protruding through aliquid-sealed orifice (e.g., 24 in FIG. 1). A liquid/gas separationvessel was connected to the bottom of the reaction tube (e.g., 10 inFIG. 1). The excess gas flowed through to an ice condenser followed byan ozone destruction unit. The collected liquid product was pumpedthrough a peristaltic pump to sampling containers for analysis.

The gas inlet (e.g., 12 in FIG. 1) was connected to an Ozonia OzatCFS-2G ozone generator and the liquid inlet was connected to a stirredfeed tank equipped with a peristaltic pump. The liquid inlet pipe wasalso jacketed and cooled to control the temperature of the feed liquidreagent.

Ozonolysis Reagent and Product Details

Methoxycitronellene was >99% pure and was obtained from reaction ofmethanol with dihydromyrcene. Fatty acid methyl esters (FAME) wasobtained from multiple sources including soy, palm, and algal oils andconsisted of 72-89% methyl oleate as the primary component.

When methoxycitronellene is reacted, the major product ismethoxymelonal. When FAME is reacted, the major products are methylazelaldehyde and nonanal.

For the emulsion preparation, water was combined with the organicreagent in a 5:1 ratio in the feed tank and stirred vigorously such thata homogenous emulsion was maintained. Deionized water was used for allof the emulsions.

A mixture of 95% O₂ and 5% N₂ gas was used to feed the ozone generatorand to comprise the carrier gas for O₃ to the reaction.

Conversions of starting materials were determined by GC (Agilent 6890N)and were calculated based on the disappearance of the starting materialon a gross adjusted basis. Samples were prepared by extracting theorganic components of the emulsion into a homogenous ethyl acetatesolvent phase and analyzing the composition of said organic phase by gaschromatography.

Example reaction conditions and product distributions are outlined inTables 1 and 2. Reactions were performed at various O₃ concentrationsand mass flow rates.

TABLE 1 Methoxycitronellene in a water-based emulsion was oxidized byozonolysis at different ozone concentrations and flow rates to yield thestarting material conversion percentages shown. Ratio Conver- of WaterO₃ Gas O₃ sion of to Conc Flow- Mass Emulsion Cooling Starting Organic(w/w) rate Flow Flow Temp Material Sample Reagent % L/min g/h kg/h ° C.% 1 5:1 2.5 15 32.6 2 10 13.70 2 5:1 2.5 15 32.6 2 10 15.79 3 5:1 5 1565.9 2 10 26.76 4 5:1 5 15 65.9 2 10 24.71 5 5:1 10 15 135 2 10 48.89 65:1 10 15 135 2 10 52.63

TABLE 2 FAME (89% methyl oleate) in a water-based emulsion was oxidizedby ozonolysis at different ozone concentrations and flow rates to yieldthe starting material conversion percentages shown. Ratio Conver- ofWater O₃ Gas O₃ sion of to Conc. Flow- Mass Emulsion Cooling StartingOrganic (w/w) rate Flow Flow Temp Material Sample Reagent % L/min g/hkg/h ° C. % 1 5:1 4   15 52.5 2 25 42.4 2 5:1 4   15 52.5 2 25 38.8 35:1 6.4 15 85 2 25 46.5 4 5:1 6.4 15 85 2 25 50.4 5 5:1 9.5 15 128 2 2550.9 6 5:1 9.5 15 128 2 25 51.3

Example 2 Ozonolysis Reactor 2 Details

A second arrangement of involving 3 pilot tube reactors connected inseries was used. All 3 tubes were 1.7 m in length, with the first 2tubes being 25 mm in diameter and the 3^(rd) tube being 10 mm indiameter. All tubes were equipped with a film distribution head, acooling jacket, and a gas liquid separator at the bottom. The organic,liquid feed was flowed from the first tube through the second and thirdtube in series. The gas was flowed co-currently from the 3^(rd) tubethrough the 2^(nd) to the 1^(st) tube. The cooling jacket temperaturewas maintained at 15° C.

In one instance, this reactor was used to process a 75% mixture ofvegetable fatty acid in nonanoic acid. The major components of thevegetable fatty acid were estimated as follows: 77.65% oleic acid,11.64% linoleic acid, 1.98% stearic acid, 4.4% palmitic acid, 2.9%myristic acid. The O₃ was generated using pure O₂ and a generatorcomposed of 2 Pinnacle Quadblocks in a custom cabinet. The results ofthis run are presented in Table 3.

TABLE 3 Ozonolysis of vegetable fatty acid in a film ozonolysis reactor.Sample 1 was taken at 10 minutes, Sample 2 at 15 minutes, and Sample 3at 20 minutes. Conversion was based on disappearance of startingmaterial on GC FID as compared to an internal standard. Ratio ofConversion Vegetable of Starting Fatty O₃ Gas O₃ Material Acid to Conc.Flow- Mass Liquid Cooling (oleic/ Nonanoic (w/w) rate Flow Flow Templinoleic) Sample Acid % L/min g/h kg/h ° C. % 1 3:1 5.1 150 672 4.2 1595.5/98.1 2 3:1 5.1 150 672 4.2 15 94.0/97.6 3 3:1 5.1 150 672 4.2 1593.7/97.3

In another instance, this reactor was used to convert a 25% solution ofdihydromyrcenol in water to hydroxymelonal. The results of this run areshown in Table 4.

TABLE 4 Ozonolysis of dihydromyrcenol, i.e., hydroxycitronellene, in thefilm ozonolysis reactor to generate hydroxymelonal. Samples were takenevery 5 minutes. Conversion was based on GC FID results. Conver-Dihydro- O₃ sion of myrcenol Gas Mass Liquid Cooling Starting to WaterO₃ % flow Flow Flow Temp Material Sample Ratio (w/w) (L/min) (g/hr)(ml/min) (° C.) % 1 3:1 7.8 80 555.8 80 5-15 99.8 2 3:1 7.8 80 555.8 805-15 99.5 3 3:1 7.8 80 555.8 80 5-15 98.5 4 3:1 7.8 80 555.8 80 5-1597.2 5 3:1 7.8 80 555.8 80 5-15 98.3

Similar results were obtained for the conversion of β-lonone to generatecyclocitral.

INCORPORATION BY REFERENCE

The entire disclosure of each of the patent documents and scientificarticles referred to herein is incorporated by reference for allpurposes.

EQUIVALENTS

The disclosure can be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The foregoingembodiments are therefore to be considered in all respects illustrativerather than limiting on the disclosure described herein. Scope of thedisclosure is thus indicated by the appended claims rather than by theforegoing description, and all changes that come within the meaning andrange of equivalency of the claims are intended to be embraced therein.

What is claimed is:
 1. A method of performing ozonolysis or ozone-basedoxidation on a liquid or emulsified reagent using a tubular falling filmreactor with one or multiple tubes wherein the combined ozone andcarrier gas flow is co-current.
 2. The method of claim 1, wherein thediameter of the tube(s) is between 5 mm and 5 m.
 3. The method of claim2, wherein the diameter of the tube(s) is between 5 and 30 mm.
 4. Themethod of claim 2, wherein the diameter of the tube(s) is between 5 and50 mm.
 5. The method of claim 2, wherein the diameter of the tube(s) isbetween 50 mm and 5 m.
 6. The method of claim 1 where the tube diameteris between 50 mm and 5 m and an annular element is added in to regulategas flow and to add additional film surface area.
 7. The method of anyone of claims 1-6, wherein the length of the tube(s) is between 1 and 20m.
 8. The method of claim 7, wherein the length of the tube(s) isbetween 1 and 7 m.
 9. The method of claim 8, wherein the length of thetube(s) is 1.7 m.
 10. The method of claim 8, wherein the length of thetube(s) is 6 m.
 11. The method of claim 7, wherein the length of thetube(s) is between 7 and 20 m.
 12. The method of any one of claims 1-11,wherein the distribution of gas within the tube(s) may be controlled byannular spaces for gas flow within the tube(s).
 13. The method of anyone of claims 1-12, wherein multiple falling film tube reactors are usedin series to process a continuous stream of liquid or emulsifiedreagent.
 14. A method of performing ozonolysis or ozone-based oxidationon a liquid or emulsified reagent with a gaseous reagent comprisingozone and one or more carrier gases, the method comprising: (a) feedingthe liquid or emulsified reagent from a common liquid or emulsifiedreagent feeding chamber that is maintained completely full throughannular slots and into a plurality of parallel and substantiallyidentical tubes, as to form a liquid or emulsified reagent film on theinternal surface of each tube; (b) feeding the gaseous reagent throughthe annular slots and into the tubes from a gaseous reagent feedingchamber, the feeding pressure of the gaseous reagent being substantiallythe same as the pressure loss from the gaseous reagent flow through thetubes containing the liquid or emulsified reagent film, but less thanthe feeding pressure of the liquid or emulsified reagent; and (c)cooling the tubes by flowing a liquid coolant through a housingsurrounding the tubes.
 15. The method of claim 14, further comprising(d) collecting reaction product(s) and gaseous reagent exhaust in one ormore product containers connected to the end of the tubes opposite thatconnected to the annular slots.
 16. The method of claim 14, wherein thelength of the tubes is between 1 and 20 m.
 17. The method of claim 16,wherein the length of the tubes is between 1 m and 7 m.
 18. The methodof claim 17, wherein the length of the tubes is 1.7 m.
 19. The method ofclaim 17, wherein the length of the tubes is 6 m.
 20. The method ofclaim 16, wherein the length of the tubes is between 7 m and 20 m. 21.The method of any one of claims 14 through 16, wherein the internaldiameter of the tubes is between 5 mm and 5 m.
 22. The method of claim21, wherein the internal diameter of the tubes is between 5 mm and 30mm.
 23. The method of claim 21, wherein the internal diameter of thetubes is between 5 mm and 50 mm.
 24. The method of claim 21, wherein theinternal diameter of the tubes is between 50 mm and 5 m.
 25. The methodof any one of claims 14 through 24, wherein the feeding pressure of thegaseous reagent is between 0.1 and 5 bar.
 26. The method of claim 25,wherein the feeding pressure of the gaseous reagent is between 0.1 and0.5 bar.
 27. The method of claim 26, wherein the feeding pressure of thegaseous reagent is between 0.2 and 0.4 bar.
 28. The method of any one ofclaims 14 through 27, wherein the feeding overpressure of the liquid oremulsified reagent with respect to the feeding pressure of the gaseousreagent is between 5 and 15 cm of liquid column.
 29. The method of anyone of claims 14 through 28, wherein the carrier gas contains, at leastin part, gaseous reagent exhaust from one or more product containers.30. The method of claim 1 as described herein with reference to theaccompanying drawings and examples.
 31. The method of any one of claims1 through 29, wherein the liquid or emulsified reagent compriseshydroxycitronellene.
 32. The method of claim 31, wherein the liquid oremulsified reagent is a hydroxycitronellene emulsion in water.
 33. Themethod of claim 31, wherein the liquid or emulsified reagent is ahydroxycitronellene solution in methanol.
 34. The method of any one ofclaims 31 through 33, wherein the product is hydroxymelonal.
 35. Themethod of any one of claims 1 through 29, wherein the liquid oremulsified reagent comprises methoxycitronellene.
 36. The method ofclaim 35, wherein the liquid or emulsified reagent is amethoxycitronellene emulsion in water.
 37. The method of claim 35,wherein the liquid or emulsified reagent is a methoxycitronellenesolution in methanol.
 38. The method of any one of claims 35 through 37,wherein the product is methoxymelonal.
 39. The method of any one ofclaims 1 through 29, wherein the liquid or emulsified reagent comprisesfatty acid methyl esters (FAME).
 40. The method of claim 39, wherein theliquid or emulsified reagent is a FAME emulsion in water.
 41. The methodof claim 39, wherein the liquid or emulsified reagent is a FAME solutionin methanol.
 42. The method of any one of claims 39 through 41, whereinthe product comprises methyl azealdehyde and nonanal.
 43. The method ofany one of claims 1 through 29, wherein the liquid or emulsified reagentcomprises an unsaturated olechemical such as a triglyceride, a fattyacid, a fatty alcohol, or a fatty acid ester.
 44. The method of any oneof claims 1 through 29, wherein the liquid or emulsified reagentcomprises a diterpene.
 45. The method of claim 44, wherein the diterpeneis abietic acid or its ester.
 46. The method of any one of claims 1through 29, wherein the liquid or emulsified reagent comprises a mono-or di-unsaturated sesquiterpene.
 47. The method of any one of claims 1through 29, wherein the liquid or emulsified reagent comprises a mono-or di-unsaturated monoterpene or terpene derivative.
 48. The method ofclaim 47, wherein the mono- or di-unsaturated monoterpene or terpenederivative is pinene or limonene.
 49. The method of any one of claims 1through 29, wherein the liquid or emulsified reagent comprises an allylether of 10 to 30 carbon atoms.
 50. The method of any one of claims 1through 29, wherein the liquid or emulsified reagent comprises an alphaolefin of 10 to 30 carbon atoms.
 51. The method of any one of claims 1through 29, wherein the liquid or emulsified reagent comprises atertiary amine.
 52. The method of claim 51, wherein the product is anN-oxide derivative.
 53. The method of any one of claims 1 through 29,wherein the liquid or emulsified reagent comprises a rose ketone. 54.The method of claim 53, wherein the rose ketone is Ionone.
 55. Themethod of claim 54, wherein the product is cyclocitral.
 56. The methodof any one of claims 1 through 29, wherein waste water is the reagentintroduced into the reactor for the purpose of treating the waste water.57. The method of any one of claims 1 through 29, wherein the reagentintroduced into the reactor is any compound that is susceptible to ozoneoxidation.
 58. The method of claim 57, wherein the reagent is selectedfrom the group consisting of an alkane, an amide, a carboxylic acid, anda compound containing an aromatic ring.
 59. The method of any one ofclaims 1 through 29, wherein the carrier gas is O₂.
 60. The method ofany one of claims 1 through 29, wherein the carrier gas is air.
 61. Themethod of any one of claims 1 through 29, wherein the carrier gas is amixture of O₂ and N₂.
 62. The method of claim 61, wherein the carriergas is about 95% O₂ and about 5% N₂.